EP0589364B1 - Ethylen-Olefin-Kopolymere, Verfahren zur Herstellung derselben mit Katalysator - Google Patents

Ethylen-Olefin-Kopolymere, Verfahren zur Herstellung derselben mit Katalysator Download PDF

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Publication number
EP0589364B1
EP0589364B1 EP93114988A EP93114988A EP0589364B1 EP 0589364 B1 EP0589364 B1 EP 0589364B1 EP 93114988 A EP93114988 A EP 93114988A EP 93114988 A EP93114988 A EP 93114988A EP 0589364 B1 EP0589364 B1 EP 0589364B1
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EP
European Patent Office
Prior art keywords
copolymers
ethylene
alpha
copolymer
compound
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EP93114988A
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English (en)
French (fr)
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EP0589364A2 (de
EP0589364A3 (de
Inventor
Luigi Resconi
Tiziano Dall'occo
Fabrizio Piemontesi
Floriano Guglielmi
Enrico Albizzati
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Basell Polyolefine GmbH
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Basell Polyolefine GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers

Definitions

  • the present invention relates to ethylene copolymers, characterized by an extremely dispersed distribution of comonomers, a process for the preparation of the mentioned ethylene copolymers and the catalytic system used in said process.
  • polyethylene can be modified, during the polymerization reaction, by addition of small amounts of alpha-olefins, generally 1-butene, 1-hexene or 1-octene.
  • alpha-olefins generally 1-butene, 1-hexene or 1-octene.
  • LLDPE copolymers linear low density polyethylene are obtained which show branching along the main chain due to the alpha-olefinic comonomers.
  • the percentage of the incorporated alpha-olefin affects the degree of crystallinity and, consequently, the density of the copolymer.
  • the LLDPE polyethylene has density of the order of 0.915-0.940 g/cm 3 and, for density of 0.915 g/cm 3 , the alpha-olefin content is higher than 5% by mol.
  • the properties of the copolymer also depend on the distribution of branching along the polymeric chains.
  • the higher distribution homogeneity of branching has a positive effect on the characteristics of films obtained from the copolymers.
  • LLDPE copolymers prepared with conventional Ziegler-Natta catalysts are characterized by poorly dispersed composition, and in particular by the presence of consecutive units of the comonomers in the polymeric chain. Therefore, in order to obtain copolymers endowed with low enough density and crystallinity, it is necessary to use high amounts of alpha-olefinic comonomer.
  • European Patent application No. 452920 describes "random" copolymers of ethylene with an alpha-olefin endowed with close composition distribution and improved "melt tension". Said copolymers are prepared using a catalyst which comprises the product of the prepolymerization reaction of the olefin with:
  • component [C] ethylene bis-indenyl zirconium dichloride has been used.
  • EP-A-0 575 875 describes catalyst systems comprising the product obtained by contacting a titanium, zirconium or hafnium mono or bis-cyclopentadienyl compound; an alkyl aluminium wherein at least one alkyl is different from a straight alkyl; and water. These catalyst systems are active in general in the polymerization of olefins.
  • EP-A-0 513 380 discloses a process for the homo and copolymerization of ⁇ -olefins, carried out in the presence of a catalyst system comprising: a transition metal compound, a compound which forms an anionic complex by reaction with said transition metal compound, and an organoaluminum compound.
  • the ethylene copolymers comprise units deriving from ethylene and units deriving from at least a comonomer selected from 1-butene and 1-hexene having content of units deriving from alpha-olefin, comprised between 1 by mol and 10% by weight, having a solubility in xylene of 25°C lower than 2% by weight and are characterized by the fact that the molar percentage of the alpha-olefinic comonomer (% ⁇ ) and the density of the copolymer (D) satisfy the relation: % ⁇ + 150D ⁇ 140
  • Super random copolymers are characterized by an extremely dispersed distribution of the comonomers along the polymeric chain and, more particularly, by the fact that they contain an extremely low number of sequences of two or more equally consecutive units of comonomer, lower than that of a "random" copolymer.
  • copolymers according to the invention are characterized by relatively low values of the solubility in xylene at 25°C (lower than 2% by weight for a content of alpha-olefinic comonomer up to 10% by weight).
  • the alpha-olefinic comonomer is 1-butene
  • the percentage by weight of 1-butene (%B) and the density of the copolymer (D) satisfy the relation: % B + 300 D ⁇ 282.
  • the ethylene copolymers according to the present invention can be prepared by the copolymerization reaction of ethylene with at least one comonomer selected from 1-butene and 1-hexene said process being carried out in the presence of catalyst systems obtained from the product of the reaction between:
  • the molar ratio between the organometallic aluminium compound and water is higher than 1:1 and lower then about 100:1.
  • the preferred molar ratio is higher than about 2:1 and lower than about 50:1.
  • the molar ratio between the aluminium and zirconium is comprised between about 100 and 5000, and preferably between about 500 and 2000.
  • the polymerization reaction according to the invention can be carried out in liquid phase, optionally in the presence of an inert hydrocarbon solvent, or in the gas phase.
  • a remarkable operative advantage of the process of the present invention resides in the fact that it can be suitably carried out in liquid phase without using an aromatic solvent such as toluene.
  • the copolymerization reaction can be carried out in the presence of aliphatic or alicyclic hydrocarbon solvents. Good results are obtained by working, for example, in liquid propane.
  • the most preferred zirconocene compound is the dimethylsilandiyl-bis(tetramethylcyclopentadienyl)zirconium dichloride.
  • all the substituents R 2 of the organometallic aluminium compound are non linear alkyl, alkenyl or alkylaryl radicals. More preferably, all the substituents R 2 of the organometallic aluminium compound are isoalkyl radicals.
  • Particularly preferred compound is the triisobutyl aluminium (TIBAL).
  • a particular reaction product of TIBAL with water which can be suitably used such as catalyst component (B), is the tetraisobutyl alumoxane (TIBAO).
  • the alkyl aluminium compound can be reacted with water in different manners. It is possible, for example, to add the water gradually to the alkyl aluminium compound in solution in an inert aliphatic or aromatic hydrocarbon solvent such as, for example, heptane or toluene.
  • the water can be introduced into the monomer or one of the monomers to be polymerized; in this case the alkyl aluminium compound and the metallocene are precontacted before being used in the polymerization.
  • the water can be reacted in combined form as hydrated salt, or it can be adsorbed or absorbed on an inert support, such as silica.
  • Another preparation method is the reaction of the alkyl aluminium with boric anhydride or with boric acid.
  • the catalysts used in the process of the present invention can be also used on inert supports. This is obtained by depositing the metallocene compound, or the product of the reaction of the same with the alkyl aluminium pre-reacted with water, or the aluminium alkyl compound pre-reacted with water and thereafter the metallocene compound, on inert supports such as for example silica, alumina, styrene-divinylbenzene copolymers or polyethylene.
  • the polymerization temperature is generally comprised between 0°C and 250°C, and in particular between 20°C and 150°C, and more particularly between 40°C and 90°C.
  • the molecular weight of the copolymers can be simply changed varying the polymerization temperature, the type or concentration of the catalytic components or using molecular weight regulators such as, for example, hydrogen.
  • the molecular weight distribution can be varied using mixtures of different metallocenes, or carrying out the polymerization in many steps which differ in the polymerization temperatures and/or the concentration of the molecular weight regulator.
  • the contact time is generally comprised between 1 and 60 minutes, preferably between 5 and 20 minutes.
  • the pre-contact concentrations for the metallocene compound are comprised between 10 -2 and 10 -8 mol/l, whereas for the product of the reaction between the alkyl aluminium and the water are between 10 and 10 -3 mol/l.
  • the pre-contact is generally carried out in the presence of a hydrocarbon solvent and, optionally, small amounts of monomer.
  • the intrinsic viscosity (I.V.) has been measured in tetrahydronaphtalene at 135°C.
  • the Melt Index (MI) has been measured under the following conditions:
  • the percentage by weight of comonomers in the copolymer is determined according to Infra-Red (IR) techniques.
  • the real density has been measured according to the ASTM D-1505 method by deeping of an extruded polymer sample in a density gradient column.
  • DSC Differential Scanning Calorimetry
  • the solubility in xylene at 25°C has been determined according to the following modalities. About 2.5 g of polymer and 250 ml of xylene are placed in a round-bottomed flask provided with cooler and reflux condenser, kept under nitrogen head. This is heated to 135°C and is kept stirred for about 60 minutes. This is allowed to cool under stirring to 25°C.
  • the whole is filtered off and after evaporation of the solvent from the filtrate until a constant weight is reached, the weight of the soluble portion is calculated.
  • the catalyst component (A) has been synthetized as follows:
  • the flask was cooled to 0°C on a ice bath and very slowly 100 ml of water and then 100 ml of 10% sulfuric acid were added: separation in two layers was obtained.
  • the aqueous layer was extracted three times with ether, the organic phases were collected, washed first with a saturated solution of sodium bicarbonate and then with water and dried on anhydrous sodium sulfate.
  • the ether solution was concentrated to 700 ml and transferred into a 1 liter round-bottomed flask provided with mechanical stirrer and cooler with 6.15 g (32.3 mmol) of p-toluensulfonic acid monohydrate. This was kept under stirring for 3 hours at room temperature.
  • the temperature was brought to 0°C and 165 ml of n-butyllithium (1.6 M in hexane, 264 mmol) were added dropwise over one and a half hours.
  • the catalyst component (B) has been synthetized as follows:
  • the polymer was separated by washing with methanol and drying under vacuum.
  • the example was carried out according to example 3, but with the difference that the zirconocene compound was fed with subsequent additions of 1/4, 1/4 and 1/2 of the total amount.
  • the present invention allows LLDPE copolymers having low values of density, crystallinity degree and melting temperature to be obtained using the minimum of alpha-olefinic comonomers.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Polyethers (AREA)
  • Lubricants (AREA)
  • Detergent Compositions (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Claims (1)

  1. Copolymer von Ethylen mit mindestens einem unter 1-Buten und 1-Hexen ausgewählten α-olefinischen Comonomer mit einem Gehalt an Einheiten, die sich von den α-olefinischen Comonomeren ableiten, zwischen 1 Mol-% und 10 Gew.-%, und einer Löslichkeit in Xylol bei 25°C von weniger als 2 Gew.-%, dadurch gekennzeichnet, daß der Molprozentanteil an α-olefinischem Comonomer (% α) und die Dichte des Copolymers (D) der folgenden Beziehung genügen: %  α + 150  D ≤ 140.
    Figure imgb0009
EP93114988A 1992-09-24 1993-09-17 Ethylen-Olefin-Kopolymere, Verfahren zur Herstellung derselben mit Katalysator Revoked EP0589364B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI922180 1992-09-24
ITMI922180A IT1255514B (it) 1992-09-24 1992-09-24 Copolimeri dell'etilene con monomeri olefinici, processo per la loro preparazione e catalizzatore

Publications (3)

Publication Number Publication Date
EP0589364A2 EP0589364A2 (de) 1994-03-30
EP0589364A3 EP0589364A3 (de) 1994-08-03
EP0589364B1 true EP0589364B1 (de) 2006-01-11

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EP93114988A Revoked EP0589364B1 (de) 1992-09-24 1993-09-17 Ethylen-Olefin-Kopolymere, Verfahren zur Herstellung derselben mit Katalysator

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EP (1) EP0589364B1 (de)
JP (1) JP3461539B2 (de)
KR (1) KR100294783B1 (de)
CN (1) CN1050141C (de)
AT (1) ATE315593T1 (de)
AU (1) AU672425B2 (de)
BR (1) BR9303880A (de)
CA (1) CA2106733C (de)
DE (1) DE69333963T2 (de)
ES (1) ES2256835T3 (de)
FI (1) FI934167A (de)
IT (1) IT1255514B (de)
NO (2) NO303341B1 (de)
PL (1) PL173769B1 (de)
RU (1) RU2140930C1 (de)
ZA (1) ZA937012B (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1270253B (it) * 1994-06-20 1997-04-29 Spherilene Srl Copolimeri dell'etilene e procedimento per la preparazione di polimeri dell'etilene
FI970349A (fi) * 1997-01-28 1998-07-29 Borealis As Uudet metalloseeniyhdisteiden aktivaattorisysteemit
US5866706A (en) * 1997-06-09 1999-02-02 Boulder Scientific Co. Preparation and separation of RAC and MESO compound mixtures
US6960634B2 (en) * 2001-10-31 2005-11-01 Univation Technologies, Llc Methods for adjusting melt properties of metallocene catalyzed olefin copolymers
EP1803747A1 (de) 2005-12-30 2007-07-04 Borealis Technology Oy Oberflächemodifizierte Polymerisationskatalysatoren zur Herstellung von Polyolefinfilmen mit niedrigem Gelgehalt
KR101561381B1 (ko) 2014-02-05 2015-10-16 주식회사 엘지화학 폴리부텐-1 단독 중합체 또는 공중합체의 제조방법
KR101747401B1 (ko) * 2014-12-08 2017-06-14 주식회사 엘지화학 가공성이 우수한 에틸렌/알파-올레핀 공중합체

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0780933B2 (ja) * 1986-11-20 1995-08-30 三井石油化学工業株式会社 オレフインの重合方法
IT1237398B (it) * 1989-01-31 1993-06-01 Ausimont Srl Catalizzatori per la polimerizzazione di olefine.
US5369196A (en) * 1990-11-30 1994-11-29 Idemitsu Kosan Co., Ltd. Production process of olefin based polymers
DE69329170T2 (de) * 1992-06-18 2001-03-29 Montell Technology Co. B.V., Hoofddorp Katalysator zur Olefinpolymerisation

Also Published As

Publication number Publication date
PL173769B1 (pl) 1998-04-30
KR940007072A (ko) 1994-04-26
RU2140930C1 (ru) 1999-11-10
EP0589364A2 (de) 1994-03-30
ES2256835T3 (es) 2006-07-16
ITMI922180A0 (it) 1992-09-24
FI934167A0 (fi) 1993-09-23
ZA937012B (en) 1994-04-18
CA2106733A1 (en) 1994-03-25
DE69333963D1 (de) 2006-04-06
IT1255514B (it) 1995-11-09
CN1088588A (zh) 1994-06-29
NO933386L (no) 1994-03-25
BR9303880A (pt) 1994-06-21
AU4756993A (en) 1994-03-31
CA2106733C (en) 2009-05-12
NO303341B1 (no) 1998-06-29
JPH06192340A (ja) 1994-07-12
NO980486L (no) 1994-03-25
DE69333963T2 (de) 2006-08-24
CN1050141C (zh) 2000-03-08
PL300469A1 (en) 1994-04-18
FI934167A (fi) 1994-03-25
NO980486D0 (no) 1998-02-04
NO933386D0 (no) 1993-09-23
EP0589364A3 (de) 1994-08-03
AU672425B2 (en) 1996-10-03
ITMI922180A1 (it) 1994-03-24
ATE315593T1 (de) 2006-02-15
KR100294783B1 (ko) 2001-09-17
JP3461539B2 (ja) 2003-10-27

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